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Zn2tio4 Nano2
Zn2tio4 Nano2
a
Study and Research of Condensed Statements Laboratory (LEREC), Badji Mokhtar University,
Annaba- B.P.12, ANNABA 23000, ALGERIA
b
Inorganic Materials Chemistry Laboratory (LCMI), Badji Mokhtar University, Annaba- B.P.12,
ANNABA 23000, ALGERIA
c
European Institute of Membranes, UMR 5635 CNRS ENSCM University Montpellier,
Place Eugene Bataillon, F-34095 MONTPELLIER CEDEX 5, FRANCE
ABSTRACT
This paper reports the synthesis and the characterization of 1D Zinc titanate nanobelts of different
molar ratios Zn/Ti = 0.26-0.40-0.80 (Zn(CH3COO)2/TTIP) prepared by electrospinning. The samples were
annealed at 600°C and 900°C temperatures in air for 5 hr. The as-spun and annealed (Zn(CH3COO)2/
TTIP)/PVP composite nanobelts were characterized by scanning electron microscopy (SEM), Energy-
dispersive X-ray spectroscopy analysis (EDX), X-ray diffraction (XRD), Raman spectroscopy and
photoluminescence (PL). The results in this paper demonstrate that heat treatment has an influence on the
process of crystallization. According to the X-ray diffraction, the formation of ZnTiO3 rhombohedral
phase. Raman spectroscopy results confirm the formation of ZnTiO3 phase. They are in good agreement
with the X-ray diffraction. Photoluminescence reveals that high quantity of Titanium makes shift from
emitted bands to greater wavelengths (visible region). However, high temperature causes a shift from
emission bands to greater wavelengths and regeneration of other bands.
Key words: Titanium oxide, Zinc oxide, Electrospinning, 1D, Nanobelts, Photoluminescence.
INTRODUCTION
Tansparent conductive oxides (TCO) such as Zinc oxide (ZnO) and titanium oxide
(TiO2) have attracted considerable attention in different fields such as photovoltaic1,2
optoelectronics3, touch screens4, electrochromic devices5 and flat panel displays6-8 and due
________________________________________
*
Author for correspondence; E-mail: achraf_hamrouni58@yahoo.fr
672 A. Hamrouni et al.: Structural and Optical Properties of….
to their transparency to visible light and good conductivity9. The elaboration of such
materials at nanoscale such as one-dimensional nanostrcutures10-13 have attracted many
researchers because of their outstanding physical and chemical properties.
Since 1960s many researchers have been interested in Zinc titanate (ZnTiO3)
materials and its characterizations. It has three crystalline phases: ZnTiO4 (CFC), ZnTio3
(hexagonal) and Zn2Ti3O8 (cubic), and undergoes many transformations at different
temperatures. At a temperature, superior than about 800°C, ZnTi3O8 is decomposed into
ZnTiO3 and rutile TiO2 phase. At about 945°C, ZnTiO3 is decomposed into Zn2TiO4, while
TiO2 rutile is a stable phase and an important photocatalytic material16.
EXPERIMENTAL
stirred for 15 min at room temperature to obtain sufficient viscosity required for
electrospinning. The electrospinning solutions were placed into a 22 mL syringe with a 25
gauge stainless steel needle at the tip. The syringe pump was adjusted to 0.3 mL/hr of
feeding rate. Then, the electric voltage of 30 kv was applied between the needle and the
collector. The distance between the tip of the syringe needle and the collector (Al plate) was
fixed to 17 cm. The samples were left overnight in air to fully hydrolyze. To remove the
polymer and achieve crystallinity, the composite were then treated in air at different
temperatures 600oC, and 900oC for 5 hr with a heating rate of 2°C/min. The microstructures,
the phase and the crystal structure of the 1D nanostructures synthesized were analysed using
scanning electron microscopy (SEM, Hitachi S-4800), X-ray diffraction (Panalyticalxpert-
PRO diffractometer equipped with ax’celerator detector using Ni-filtered Cu-radiation),
Raman (Jobin-Yvon S. A., Horiba, France) and Energy-dispersive X-ray spectroscopy
analysis (Zeiss EVO ED15 microscope coupled with an Oxford X-maxn EDX detector).
Photoluminescence of 1D nanostructures was measured at room temperature using the
experimental setup, described elsewhere by Chaaya et al.23 The PL was excited by solid state
laser (355 nm) and the emission spectra were recorded in the range 360-800 nm.
Cont…
674 A. Hamrouni et al.: Structural and Optical Properties of….
EDS analysis shown in Table 1 reveals the presence of Ti, Zn and O. No other
elements are present in the sample. This confirms that heat treatment at 600oC and 900oC
removes PVP, DMF and ethanol completely from the nanobetls. The X-ray diffraction
indicates the formation of zinc titanate oxide ZnTiO3 rhombohedrique for different ratio
molars at 600oC and 900oC. At 600oC Fig. 2(a) and for different ratio molars, there is a
formation of ZnTiO3 phase; i. e. the variation of ratio molar does not influence on the
formation of ZnTiO3 phase. Group space is G.S: R3 (148), lattice parameters a = b = c =
5.07 and angle α = β = γ ≠ 90°. It is justified by the presence of the most intense peaks (104)
and (110) were observed at 2θ = 32.84° and 2θ = 35.20°, respectively, while the weak peaks
at 23.82°, 40.29°, 41.14°, 48.76°, 53.34°, 56.69°, 61.73°, 63.25° and 68.89° correspond to
(012), (113), (021), (024), (116), (018), (214), (300) and (112), respectively. This results are
in good agreement with what is reported in the map data JCPDS [26-1500]. This formation
is due to the reaction between zinc oxide and titanium oxide obtained by the decomposition
of organometallic precursors at 345°C16. However, ZnTiO3 starts to crystalize at 450oC16.
The appearance of pics ZnO hexagonal phase25 and TiO2 rutile-anatase phases25 with
different proportions is due to variation of molar ratio between the samples. Appearance of
Zn2TiO4 cubic phase when Zn/Ti = 0.4 and in existence when Zn/Ti = 0.26 and 0.8, which is
justified by the effect of the amount of Ti, which was different to Zangying et al. report. In
the report of Zangying et al. is mentioned temperature less than 885°C. ZnTiO3 exists and
decomposes at temperature more than 900°C to Zn2TiO4 and TiO2 rutile, which are different
from our results is due to time of calcination chosen and the amount of Titanium because
there is no formation of Zn2TiO4 at 600°C after 1.5 hr of calcinations16. At 900°C Fig. 2(b),
complete formation of ZnTiO3 rhombohedral phase, transformation of TiO2 anatase to TiO2
rutile, there is a ZnO trace and TiO2 anatase. In existence of Zn2TiO4 phase after calcination
Int. J. Chem. Sci.: 14(2), 2016 675
is different to Zanying report, which is different of our results. The absence Zn2Ti3O8 phase
is similar to Zanying et al.16 report and different to How26.
Intensity u.a.
A
°
° °
R
A
°
A
R
. *
°°
°
°
*°
°
°
°
° °
°
°
°°
°
° 1
° R °
* ° ° 2
°° °° ° ° °° ° 3
20 30 40 50 60 70
o
2θ( )
°
*
° ° ° °
°
R ° °
° ° °
° ° °R °1
°
° ° ° 2
° ° ° 3
20 30 40 50 60 70
o
2θ( )
Fig. 2: (a) XRD patterns of different molar ratios zinc titanate ZnTiO3 nanobelts
annealed at 600°C in air for 5h. (b) XRD patterns of different molar ratios
zinc titanate ZnTiO3 nanobelts annealed at 900°C in air for 5h
Raman spectroscopy was performed for examining the formation of phase and the
vibrational modes. The ZnTiO3 nanobelts synthesized by different ratio molars and calcined
at 600oC and 900oC were examined by Raman spectroscopy. The spectra were taken at room
temperature using a 532 nm laser line as the excitation source. This technique has been able
676 A. Hamrouni et al.: Structural and Optical Properties of….
to demonstrate the formation of ZnTiO3 Rhomboedral phase. Fig. 3(a-b) shows Raman
spectra of the ZnTiO3 nanobelt calcined at 600°C, and 900°C. At 600°C [Fig. 3(a)] when
Zn/Ti = 0.26 ZnTiO3 rhomboedral structure is identified by four Raman bands at (177-231-
266-709) cm-1. The position of bands of ZnTiO3 as shown Fig. 3(a) are approximately in
good agreement with the X-ray diffraction28.
Wavenumber (cm-1)
(b)
34 4
266
177
468
612
709
231
399
144
1
Intensity u.a.
612
468
709
344
231
266
399
2
177
144
1 - Zn/Ti = 0.26
2 - Zn/Ti = 0.40
468
612
34 4
3 - Zn/Ti = 0.80
T = 900oC
231
266
144177
709
399
3
0 200 400 600 800 1000 1200
-1
Wavenumber (cm )
Fig. 3: (a) Raman spectra of ZnTiO3 nanobelts of different molar ratios annealed at
600°C in air for 5h. (b) Raman spectra of ZnTiO3 nanobelts of different
molars ratios annealed at 900°C in air for 5h
Int. J. Chem. Sci.: 14(2), 2016 677
The bands (144 (Eg)-197(Eg)-399 (B1g)-519 (B1g)-639 (A1 + B1g) represent the
vibrational modes, which are active in spectroscopy of anatase phase of TiO2.28-32
Table 1: EDX data showing the weight percent of elements of ZnTiO3 annealed at 600
and 900°C
600°C 900°C
R = 0.26 R = 0.40 R = 0.80 R = 0.26 R = 0.40 R = 0.80
Zn 07.22 10.29 14.40 06.86 09.13 13.46
Ti 27.15 25.33 18.22 28.43 26.74 19.16
o 65.63 66.02 68.38 64.71 64.10 67.38
The band at 144 cm-1 appear with a higher in intensity. The band at 345 cm-1 identify
ZnO Wurtsite structure (multiple-phonon scattering processes)27. When Zn/Ti = 0.4 and 0.80
ZnTiO3 rhomboedral structure is identified by four raman bands at (177-231-266-709) cm-1
The position of bands of ZnTiO3 as shown on Fig. 3(a) are approximately in good agreement
with the X-ray diffraction28. ZnO Wurtsite structure structure is identified by one band at
345 cm-1.27 The bands (144 (Eg)-197(Eg) -399(B1g)-519 (B1g) represent the vibrational
modes, which are active in spectroscopy of anatase phase of TiO2.28-32 and rutile has two
raman active modes detected at 447 cm-1 612 cm-1 A1g.27
At 900°C [Fig. 3(b)] in three ratio molars ZnTiO3 rhomboedral structure is identified
by six raman bands at (177-231-266-344-468-709) cm-1.28 The position of bands of ZnTiO3
as shown on Fig. 3(b) disappearance the peaks of TiO2 anatase phase in three ratio molars
and appearence one peak of rutile raman active mode at 612 cm-1 (A1g) confirm the anatase
to rutile transformation. A small peaks corresponding to (Eg) 144 cm-1 - (B1g) 399 cm-1 mode
indicating the presence of anatase phase. In our work, it was found that the formation of the
rhombohedral phase of ZnTiO3 was obtained at 600oC. However in other works, reaction
between the oxides begins at 750oC whereas at 900oC the structure crystallization28.
The photoluminescence spectrum Fig. 4 (a-b) of two ratio molars Zn/Ti = 0.26 and
Zn/Ti = 0.80 calcined at 600°C and 900°C were chosen to study the effect of the percentage
of Ti and the increase of the calcination temperature on the optical properties of ZnTiO3
nanobelts. At 600°C, when Zn/Ti = 0.26 [Fig. 4(a)], there is an appearance of one emission
band at 526 nm green region. However when the percentage of Ti decreases Zn/Ti = 0.80,
one emission band appears at 475 nm blue region. At 900°C [Fig. 4(b)], Zn/Ti = 0.26 three
bands appear: 470 nm blue region, 560 nm green region and 800 IR region.
678 A. Hamrouni et al.: Structural and Optical Properties of….
Intensity u.a.
λ (nm)
λ (nm)
Fig. 4: (a) Photoluminescence of ZnTiO3 of different molar ratios zinc titanate ZnTiO3
nanobelts annealed at 600°C. (b) Photoluminescence of ZnTiO3 of different ratio
molars zinc titanate ZnTiO3 nanobelts annealed at 900°C
When Zn/Ti = 0.80, two emission bands appear: 480 nm blue region and 740 nm red
region. Table 2 shows that the increase of Ti causes a shift from emitted band to greater
wavelengths while the increase of temperature causes a shift from emission bands to greater
wavelengths and regeneration of other bands. The emission bands: blue, green, red (visible
region) and IR are related to the following structural defects: Oxygen vacancy Vo (hole
trapes), Ti+3 Interstitials (electron trapes), Zinc vacancy (VZn) and Intertitial zinc (Zni)33,34.
Int. J. Chem. Sci.: 14(2), 2016 679
CONCLUSION
In this paper, nanobelts of zinc titanate (ZnTiO3) with three ratio molars were
produced using electrospinning method. The structure of the pure phase obtained at 600°C is
rhombohedral. It is determined by XRD and confirmed by Raman spectroscopy. The
Zn2TiO4 structure appears at 600°C when Zn/Ti = 0.40 and disappears at 900°C, which was
found different of literature. The increase of percentage of titanium in ZnTiO3 favors a shift
from emitted bands to greater wavelengths (visible region). However; high temperature
causes a shift from emission bands to greater wavelengths and regeneration of other bands.
In conclusion, that the increase of Ti rates and the calcination temperatures have useful
effect on the optical features of zinc titanate 1D nanostructures.
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